Synthesis system, rubber chemical substance for tires, synthetic rubber for tires, and pneumatic tire

ABSTRACT

The present invention provides a synthesis system that can synthesize aniline and/or styrene efficiently, a synthesis system that can synthesize butadiene (1,3-butadiene) efficiently, a rubber chemical for a tire which is synthesized from the aniline obtained by the synthesis system, a synthetic rubber for a tire which is synthesized from the styrene and/or butadiene obtained by the synthesis systems, and a pneumatic tire produced using the rubber chemical for a tire and/or the synthetic rubber for a tire. The present invention relates to a synthesis system for synthesizing aniline and/or styrene from an alcohol having two or more carbon atoms via an aromatic compound.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of U.S. application Ser. No.13/637,336, filed Sep. 25, 2012, which is the U.S. National Phase ofPCT/JP2012/051503, filed Jan. 25, 2012, which claims priority under 35U.S.C. §119(a) to Japanese Patent Application No. JP 2011-014494 filedin Japan on Jan. 26, 2011, and Japanese Patent Application No. JP2011-014495 filed in Japan on Jan. 26, 2011, the entire contents ofwhich is hereby expressly incorporated by reference.

TECHNICAL FIELD

The present invention relates to a synthesis system that can synthesizeaniline and/or styrene efficiently, a synthesis system that cansynthesize butadiene (1,3-butadiene) efficiently, a rubber chemical fora tire which is synthesized from the aniline obtained by the synthesissystem, a synthetic rubber for a tire which is synthesized from thestyrene and/or butadiene obtained by the synthesis systems, and apneumatic tire produced using the rubber chemical for a tire and/or thesynthetic rubber for a tire.

BACKGROUND ART

Aniline, a material for rubber chemicals such as antioxidants, thiazolevulcanization accelerators and sulfenamide vulcanization accelerators;and styrene and butadiene, materials for synthetic rubber such asstyrene butadiene rubber and butadiene rubber, are generally synthesizedfrom petroleum. However, fossil fuels such as petroleum and natural gasare going to be depleted, and thus a price hike of fossil fuels isexpected in the future. For this reason, consumption of fossil fuels hasbeen demanded to be reduced by increasing the yield or

From the viewpoint of utilization of natural resources, a method ofsynthesizing a vulcanization accelerator is known in which anaturally-derived long chain amine that is synthesized by reductiveamination of a saturated or unsaturated fatty acid obtained byhydrolysis of natural fat and oil is used as a material. However, thissynthesis method requires mercaptobenzothiazoles or dibenzothiazolyldisulfide in the production process, and these substances are not taughtas products from natural resources.

Examples of known synthesis methods using biomass resources as materialsinclude a method of synthesizing an aromatic compound such as benzenefrom a lower hydrocarbon such as methane contained in biogas. However,since the material is gas and thus difficult to handle, the method isstill desired to be improved. Moreover, a method using biomethanol as amaterial is also known; but this method is still desired to be improvedbecause of high toxicity of the material. Furthermore, it is difficultfor either of the methods to ensure a sufficient yield, and thusimprovement is still desired on this point.

Patent Literatures 1 and 2 disclose methods of synthesizing aniline fromglucose with microorganisms. However, these methods need someimprovement in terms of production speed, production scale or the like,and in terms of usability of various microorganism species, andproduction efficiency. Therefore, an alternative technique has beendemanded.

CITATION LIST Patent Literature

Patent Literature 1: JP-A 2010-17176

Patent Literature 2: JP-A 2008-274225

SUMMARY OF INVENTION Technical Problem

The present invention aims to solve the above problems and provide asynthesis system that can synthesize aniline and/or styrene efficiently,a synthesis system that can synthesize butadiene (1,3-butadiene)efficiently, a rubber chemical for a tire which is synthesized from theaniline obtained by the synthesis system, a synthetic rubber for a tirewhich is synthesized from the styrene and/or butadiene obtained by thesynthesis systems, and a pneumatic tire produced using the rubberchemical for a tire and/or the synthetic rubber for a tire.

The present invention also aims to provide a synthesis system that cansynthesize aniline efficiently using a biomass material, a rubberchemical for a tire which is synthesized from the aniline obtained bythe synthesis system, and a pneumatic tire produced using the rubberchemical for a tire.

Solution to Problem

A first aspect of the present invention relates to a synthesis systemfor synthesizing at least one of aniline and styrene from an alcoholhaving two or more carbon atoms via an aromatic compound.

The alcohol is preferably ethanol.

The ethanol is preferably bioethanol.

The aromatic compound is preferably benzene.

The benzene is preferably synthesized via at least one of toluene andxylene.

The aromatic compound is preferably synthesized via an alkene.

The synthesis system is preferably adapted to subject the alcohol tocatalysis by a solid acid catalyst.

The solid acid catalyst is preferably at least one selected from thegroup consisting of zeolites, alumina, and titanium compounds.

The solid acid catalyst is preferably an MFI-type zeolite.

The synthesis system is preferably adapted to subject the alcohol tocatalysis by a solid acid catalyst to give a reaction product, andcirculate the reaction product so that it is further subjected tocatalysis by the solid acid catalyst.

The synthesis system is preferably adapted to distill the reactionproduct, and circulate compounds other than a target product so thatthey are further subjected to catalysis by the solid acid catalyst.

The synthesis system is preferably adapted to distill the reactionproduct to give a distillate, cool the distillate to not higher than themelting point of benzene to recover benzene, and circulate compoundsother than the benzene so that they are further subjected to catalysisby the solid acid catalyst.

In the synthesis system, the circulation is preferably repeated.

The first aspect of the present invention also relates to a synthesissystem for synthesizing butadiene from an alcohol having two or morecarbon atoms.

The first aspect of the present invention also relates to a rubberchemical for a tire, synthesized from the aniline obtained by thesynthesis system.

The first aspect of the present invention also relates to a syntheticrubber for a tire, synthesized from at least one of the styrene obtainedby the synthesis system and the butadiene obtained by the synthesissystem.

The first aspect of the present invention also relates to a pneumatictire produced using at least one of the rubber chemical for a tire andthe synthetic rubber for a tire.

A second aspect of the present invention relates to a synthesis systemfor synthesizing aniline from a biomass material via phenol.

The biomass material is preferably a sugar or bioethanol.

The synthesis system is preferably adapted to produce the phenol by amicroorganism. Moreover, the synthesis system is preferably adapted toproduce the phenol by liquid culture of a microorganism. Here, themicroorganism producing the phenol is preferably resistant to organicsolvents.

The synthesis system is preferably adapted to produce the phenol frombioethanol as the biomass material by using a solid acid catalyst. Here,the solid acid catalyst is preferably a zeolite. Moreover, the solidacid catalyst is preferably an MFI-type zeolite.

Furthermore, the solid acid catalyst is preferably an MFI-type zeolitecarrying a member selected from the group consisting of simplesubstances of copper, titanium, platinum and ruthenium, and compoundsthereof.

The second aspect of the present invention also relates to a rubberchemical for a tire, synthesized from the aniline obtained by thesynthesis system. Here, the rubber chemical for a tire is preferablysynthesized by further using acetone obtained from a biomass material.

The acetone is preferably obtained by acetone-butanol fermentation of asugar by a microorganism. Here, the microorganism preferably belongs tothe genus Clostridium. Alternatively, the microorganism preferablyincludes a gene of the genus Clostridium introduced thereinto.

The gene preferably encodes acetoacetate decarboxylase (EC4.1.1.4),coenzyme A transferase, or thiolase.

The acetone is preferably obtained by separation from pyroligneous acid.Alternatively, the acetone is preferably derived from bioethanol.

The second aspect of the present invention also relates to a pneumatictire produced using the rubber chemical for a tire.

Advantageous Effects of Invention

The first aspect of the present invention provides a synthesis systemfor synthesizing aniline and/or styrene from an alcohol having two ormore carbon atoms via an aromatic compound; and a synthesis system forsynthesizing butadiene (1,3-butadiene) from an alcohol having two ormore carbon atoms. According to the first aspect of the presentinvention, aniline, styrene, and butadiene can be efficientlysynthesized. Therefore, use of at least one selected from the groupconsisting of the aniline, styrene, and butadiene synthesized by thesynthesis systems contributes to reduction in the amount of fossilresources used in the production of rubber chemicals for a tire,synthetic rubbers for a tire, and pneumatic tires.

The second aspect of the present invention provides a synthesis systemfor synthesizing aniline from a biomass material via phenol. The secondaspect of the present invention enables efficient synthesis of anilinein a resource-saving manner without the use of fossil fuels. Therefore,use of the aniline synthesized by the synthesis system contributes toreduction in the amount of fossil fuels used in the production of rubberchemicals for a tire and pneumatic tires.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic view showing one embodiment of an apparatus fordirectly synthesizing an aromatic compound from an alcohol.

FIG. 2 is a schematic view showing one embodiment of an apparatus(circulation type) for directly synthesizing an aromatic compound froman alcohol.

FIG. 3 is a schematic view showing one embodiment of an apparatus forsynthesizing an aromatic compound from an alcohol via an alkene.

FIG. 4 is a schematic view showing one embodiment of an apparatus(circulation type) for synthesizing an aromatic compound from an alcoholvia an alkene.

DESCRIPTION OF EMBODIMENTS

The first aspect of the present invention relates to a synthesis system(synthesis method) for synthesizing aniline and/or styrene from analcohol having two or more carbon atoms via an aromatic compound; and asynthesis system (synthesis method) for synthesizing butadiene from analcohol having two or more carbon atoms.

The alcohol having two or more carbon atoms is not particularly limited,and may be a common one. From the viewpoint of low toxicity, easytransportation, and low cost, alcohols having two to eight carbon atomsare preferred, and ethanol is more preferred. Bioethanol synthesizedfrom a biomass resource can be suitably used as the ethanol because itcan be produced without depending on fossil resources, and an increasein the yield of the aromatic compound and alkene can also be expected.

A method for producing bioethanol is explained below.

Bioethanol can be produced by reducing the molecular weight of a biomassresource (e.g. corn, sugar cane, bagasse, kenaf, legumes, straw, wheatstraw, rice hulls, thinning residues, waste wood, waste paper, wastepulp, organic urban waste) (Step 1), fermenting the resulting sugarsinto ethanol (Step 2), and separating and purifying the ethanol (Step3).

In (Step 1), for example, sugars such as hexoses and pentoses, starch,cellulose, hemicellulose, and lignin are produced from the biomassresource. These products are used directly or after selection for theethanol fermentation of (Step 2). Starch, cellulose, and hemicelluloseare preliminarily saccharified by steam treatment, hydrolysis, enzymaticdegradation, or the like, and then used for the ethanol fermentation of(Step 2).

In (Step 2), ethanol is produced from monosaccharides or the likeobtained in (Step 1) by utilizing a microorganism. Examples of usablemicroorganisms include wild strains of yeasts, Escherichia coli, andbacteria of the genus Zymomonas, and their transfectants.

In (Step 3), the resulting fermentation liquid is separated into solidcomponents and a liquid phase. Thereafter, ethanol is concentrated byrepeating evaporation and condensation in a distillation process.Moreover, further concentration using a dehydrating agent or aseparation membrane may be performed.

Suitable examples of the method for synthesizing an aromatic compoundand/or an alkene from the alcohol include subjecting the alcohol tocatalysis by a catalyst. The reaction temperature is preferably 280° C.to 500° C., and more preferably 300° C. to 460° C. The reaction may beperformed at either normal or increased pressure (preferably at 0.3 to3.0 MPaG). The feed rate of the alcohol in terms of LHSV is preferably0.1 to 3.0/hr, and more preferably 0.5 to 1.5/hr.

Examples of the catalyst include solid acid catalysts such as zeolites,alumina, titanium compounds, sulfate ion-supported zirconia, andWO₃-supported zirconia. In particular, in terms of increasing thereaction efficiency, at least one selected from the group consisting ofzeolites, alumina, and titanium compounds is preferred. Zeolites aremore preferably used alone or in combination with alumina.

In the case of synthesizing an aromatic compound from the alcohol,zeolites are particularly preferred. Moreover, zeolites havingbelow-mentioned molar ratios of SiO₂ to Al₂O₃ and below-mentioned poresizes are further preferred because such zeolites enable selectivesynthesis of target aromatic compounds such as benzene.

In the case of synthesizing an aromatic compound from the alcohol usinga combination of alumina and a zeolite, the aromatic compound can besynthesized more economically with higher efficiency by firstsynthesizing an alkene using alumina and/or a zeolite, and the like, andfurther subjecting the obtained alkene to catalysis by the zeolite andthe like.

In the case of synthesizing an alkene such as ethylene and/or butadienefrom the alcohol, alumina and/or a zeolite are/is preferably used.

Zeolites are crystalline aluminosilicates having a microporousstructure. Specific examples of zeolites include A-type zeolites, L-typezeolites, X-type zeolites, Y-type zeolites, MFI-type zeolites, MWW-typezeolites, β-type zeolites, mordenite, ferrierite, and erionite.Moreover, zeolites may be used in which aluminum atoms in the zeoliteskeleton are substituted with a member selected from the groupconsisting of metal elements other than aluminum, such as Ga, Ti, Fe,Mn, Zn, B, Cu, Pt, Re, Mo, Gd, Nb, Y, Nd, W, La, and P, and compoundsthereof. In particular, in terms of selectively producing benzene andminimizing further secondary reactions such as alkylation, MFI-typeZSM-5 and MWW-type MCM-22 are preferred.

Examples of the MFI-type zeolites include zeolites having MFI (MobilFive) structure such as ZSM-5, ZSM-8, zeta 1, zeta 3, Nu-4, Nu-5, TZ-1,TPZ-1, and TS-1. From the viewpoint of high selectivity and goodreaction efficiency, ZSM-5-type zeolites are particularly preferredamong the above examples.

Cations occupying the ion-exchangeable cation sites of zeolite are notparticularly limited, and examples thereof include hydrogen ion(proton); alkali metal ions such as lithium ion, sodium ion, andpotassium ion; alkaline earth metal ions such as magnesium ion, calciumion, strontium ion, and barium ion; transition metal ions such as ironion, and silver ion; and primary to quaternary ammonium ions. Inparticular, in terms of achieving high reaction efficiency byenhancement of the surface activity, hydrogen ion (proton) is preferred.The cations may be used alone or as a combination of two or more ofthem.

Particularly preferred among the zeolites is proton-type H-ZSM-5 havingMFI structure.

Although the molar ratio of SiO₂ to Al₂O₃ (SiO₂/Al₂O₃) in thecrystalline structure of zeolite varies depending on the particularreactor, temperature, and impurities in the materials, the molar ratiois preferably 5 to 2000, more preferably 10 to 500, still morepreferably 12 to 70, and particularly preferably 15 to 35. The molarratios in these ranges can lead to minimization of further secondaryreactions (e.g. alkylation) of the generated benzene. Based on the samereason, the crystal size of zeolite is preferably (0.001 to 50) μm×(0.01to 100) μm. The particle size of zeolite is preferably 0.1 to 50 μm, andmore preferably 1 to 20 μm. Also, the nitrogen adsorption specificsurface area of zeolite is preferably 10 to 1000 m²/g, and morepreferably 100 to 500 m²/g.

Examples of the aromatic compound synthesized from the alcohol havingtwo or more carbon atoms include benzene, toluene, xylene, ethylbenzene,diethylbenzene, and butylbenzene. In particular, in terms of efficientsynthesis of aniline or styrene, benzene and ethylbenzene are preferred,and benzene is more preferred. The benzene may be synthesized viatoluene or xylene, or via an alkene such as ethylene.

The apparatus for synthesizing the aromatic compound is not particularlylimited. For example, an apparatus may be used in which a heating deviceand a material feeding system are attached to a reaction tube or thelike carrying a catalyst. In terms of enhancing the efficiency ofconversion into a target product, the apparatus preferably includes acirculation system for subjecting the alcohol to catalysis by the solidacid catalyst to give a reaction product, and circulating the reactionproduct so that it is further subjected to catalysis by the solid acidcatalyst.

The circulation system is preferably a system which is adapted todistill the reaction product to separate a target product, and circulatecompounds other than the target product, such as high-boiling reactionproducts and gaseous reaction products which have not been distilledout, so that they are further subjected to catalysis by the catalyst.Here, in the case where the target product is benzene, a system forcooling the generated benzene to not higher than the melting point (5.5°C.) of benzene to recover benzene is more preferred from the viewpointof the efficiency of conversion into benzene. Furthermore, thecirculation system preferably repeats such a circulation.

In the case of synthesizing the aromatic compound via an alkene, fromthe viewpoint of high benzene yield and maintenance of long life of thecatalyst, the apparatus preferably includes a system including tworeaction columns coupled to each other, in which an alcohol isdehydrated to produce an alkene in the first column, and then anaromatic compound is synthesized in the second column.

The method for synthesizing aniline from the aromatic compound is notparticularly limited, and conventionally known methods may be employed.For example, mention may be made of a method including reacting benzenewith an acid mixture of concentrated nitric acid and concentratedsulfuric acid, and reducing the resulting nitrobenzene by a reductiontechnique such as Bechamp reduction or catalytic reduction.

Similarly, regarding the method for synthesizing styrene from thearomatic compound, conventionally known methods may be employed. Forexample, mention may be made of a method including ethylation of benzeneby Friedel-Crafts reaction or the like, followed by dehydrogenation ofthe resulting ethylbenzene with an iron catalyst or the like. Theethylene used in Friedel-Crafts reaction can be produced, for example,by dehydration of bioethanol, and therefore styrene can be producedwithout petroleum resources.

In the case where ethylbenzene is directly synthesized as the aromaticcompound, the ethylbenzene, as it is, is dehydrogenated to synthesizestyrene.

The second aspect of the present invention relates to a synthesis system(synthesis method) for synthesizing aniline from a biomass material viaphenol.

First, a process of biosynthesis of phenol from a biomass resource byusing a microorganism is explained.

The microorganism usable in the second aspect of the present inventionis not particularly limited as long as it can utilize a biomass resourceto biosynthesize phenol.

For example, in order to biosynthesize phenol, a biomass resource can beutilized by a microorganism obtainable by introducing a gene (tpl gene)(for example, the tpl gene listed in GenBank under accession No. D13714)encoding tyrosine phenol lyase (EC 4.1.99.2), an enzyme catalyzing areaction to produce phenol from tyrosine, into a microorganism capableof biosynthesizing tyrosine.

It should be noted that tyrosine phenol lyase is apyridoxal-5′-phosphate-dependent enzyme, and catalyzes a reaction toproduce phenol, pyruvic acid, and ammonia from tyrosine. Tyrosine phenollyase is also known as β-tyrosinase or L-tyrosine phenol lyase.

The microorganism into which the tpl gene is to be introduced is notparticularly limited as long as it can biosynthesize tyrosine. Sincealmost all microorganisms on the earth can biosynthesize tyrosine, anymicroorganism can be used. Examples thereof include microorganismsbelonging to the genus Escherichia, the genus Serratia, the genusBachillus, the genus Brevibacterium, the genus Corynebacterium, thegenus Microbacterium, the genus Pseudomonas, the genus Agrobacterium,the genus Alicyclobacillus, the genus Anabena, the genus Anacystis, thegenus Arthrobacter, the genus Azotobacter, the genus Chromatium, thegenus Erwinia, the genus Methylobacterium, the genus Phormidium, thegenus Rhodobacter, the genus Rhodopseudomonas, the genus Rhodospirillum,the genus Scenedesmus, the genus Streptomyces, the genus Synechoccus,the genus Zymomonas, or the like. Among these examples, microorganismsbelonging to the genus Pseudomonas are preferred.

In general, microorganisms may die when the concentration of thegenerated phenol is high. For this reason, the microorganism into whichthe tpl gene is to be introduced is preferably resistant to organicsolvents (especially resistant to aromatic compounds) to prevent themicroorganism from dying easily due to phenol. Examples ofmicroorganisms resistant to organic solvents include Pseudomonas putidaS12. Pseudomonas putida S12 has excellent resistance to aromaticcompounds, and can therefore be suitably used as the microorganism intowhich the tpl gene is to be introduced.

The method for introducing the tpl gene into the microorganism is notparticularly limited, and a commonly-used method may be performed undergenerally known conditions. Examples of the method include, but notlimited to, a method using calcium ions (Proc. Natl. Acad. Sci., USA,69, 2110 (1972)), a protoplast method (JP-A S63-248394), anelectroporation method (Nucleic Acids Res., 16, 6127 (1988)), a heatshock method, and a particle gun method (“Seibutsu-kagaku jikken-ho(Experimental Methods in Biochemistry) 41, Syokubutsu-Saibo KogakuNyumon (Basic Plant Cell Technology)”, Sep. 1, 1998, Japan ScientificSocieties Press, pp. 255-326).

The culture medium for culturing the microorganism into which the tplgene has been introduced is not particularly limited as long as itallows growth of the microorganism to be cultured but contains a biomassresource used as a carbon source. Ordinary culture media furthercontaining a nitrogen source, inorganic ions, and optionally an organicnutrient source may be used.

The biomass resource is not particularly limited as long as it containsa sugar. Examples thereof include rice, wheat, honey, fruits, corn,sugar cane, bagasse, kenaf, legumes, straw, wheat straw, rice hulls,thinning residues, waste wood, waste paper, waste pulp, and organicurban waste. Moreover, mention may be made of sugars such as glucose,sucrose, trehalose, fructose, lactose, galactose, xylose, mannitol,sorbitol, xylitol, erythritol, maltose, amylose, cellulose, chitin, andchitosan. Preferred among the examples are sugars.

In the second aspect of the present invention, the biomass resource maybe directly used as a carbon source. However, in the case of usingbiomass resources other than the above sugars or polysaccharides such ascellulose, chitin and chitosan, these biomass resources other than thesugars, and polysaccharides are preferably used after the molecularweight thereof is reduced because, for example, some microorganismscannot directly utilize them or some have low ability to utilize them.The method for reducing the molecular weight is not particularlylimited, and known methods (e.g. steam treatment, hydrolysis, enzymaticdegradation) may be used. Monosaccharides and the like can be obtainedby reducing the molecular weight of the biomass resource other than thesugars or polysaccharide.

Glucose is particularly preferred among the above biomass resourcesbecause it contributes to efficient production of phenol. Examples ofusable glucose include those existing naturally as glucose(monosaccharide) and those obtained by reducing the molecular weight ofbiomass resources by the above-mentioned methods and the like.

Examples of the nitrogen source include inorganic ammonium salts such asammonium sulfate and ammonium chloride; organic acid ammonium salts suchas ammonium fumarate and ammonium citrate; nitrates such as sodiumnitrate and potassium nitrate; organic nitrogen compounds such aspeptone, yeast extract, meat extract, corn steep liquor and soybeanhydrolysate; ammonia gas and ammonia water; and mixtures of these.

Furthermore, an appropriate mixture of nutrient sources used in ordinaryculture media, such as inorganic salts, trace metal salts, vitamins andhormones, may also be used.

The culture conditions are not particularly limited. For example, theculture may be performed under aerobic conditions while appropriatelycontrolling the pH in the range of 5 to 8, and the temperature in therange of 20° C. to 60° C. (preferably 20° C. to 35° C.) for about 12 to480 hours. The culture may be performed by either solid or liquidculture. From the viewpoint of efficiency, liquid culture is morepreferred. The liquid culture may be performed by any of batch culture,semi-batch culture, and continuous culture.

By culturing the microorganism, a biomass resource can be utilized tobiosynthesize phenol. Phenol may be recovered by extraction from theculture liquid or the phenol accumulated in the microorganism may beextracted.

The phenol accumulated in the culture liquid may be extracted with, forexample, an organic solvent. Examples of usable organic solventsinclude, but not limited to, diethyl ether, octanol, nonanol, dodecanol,benzene, toluene, xylene, and ethyl acetate. Furthermore, the phenolextracted with the organic solvent may be purified by a knownpurification operation such as chromatography.

The phenol accumulated in the microorganism can be obtained byultrasonic disruption of the microorganism and then extraction with theorganic solvent.

Alternatively, phenol may be recovered by removing water from theculture liquid alone or from both the culture liquid and themicroorganism, followed by extraction with an organic solvent such asethanol, and then purification.

Another method for synthesizing phenol from a biomass resource includesconversion of bioethanol to phenol by using a solid acid catalyst.Examples of the solid acid catalyst include, but not limited to, zeolitecatalysts and alumina catalysts. A plurality of catalysts may be usedstepwise or simultaneously.

The solid acid catalyst may be ion-exchanged, and may further carry amember selected from the group consisting of metals such as alkalimetals, alkaline earth metals, iron, aluminum, gallium, zinc,gadolinium, platinum, vanadium, palladium, niobium, molybdenum, yttrium,rhenium, neodymium, tungsten, lanthanum, copper, titanium, andruthenium, and compounds of these metals; and phosphorus compounds,boron compounds and the like. Solid acid catalysts carrying a memberselected from the group consisting of simple substances of copper,titanium, platinum and ruthenium, and compounds thereof, are preferred.

As the solid acid catalyst, zeolites are particularly preferred, andspecific examples thereof include A-type zeolites, L-type zeolites,X-type zeolites, Y-type zeolites, MFI-type zeolites, MWW-type zeolites,β-type zeolites, mordenite, ferrierite, and erionite. Among thezeolites, MFI-type zeolites are preferred, and ZSM-5-type zeolites areparticularly preferred. Combination use of a proton-type ZSM-5 catalystand a ZSM-5 catalyst carrying a rare earth such as gadolinium andrhenium is preferred.

Next, examples of the method for synthesizing aniline from thebiosynthesized phenol include methods in which by using variouscatalysts, the phenol is allowed to react with ammonia gas or alow-molecular amine compound to prepare aniline. Examples of thecatalysts include, but not limited to, solid catalysts such as zeolitecatalysts, niobium catalysts, titania-zirconia composite oxidecatalysts, alumina catalysts and metallosilicate catalysts, and variousinorganic acids and organic acids. A plurality of catalysts may be usedstepwise or simultaneously.

The solid catalysts may be ion-exchanged, and may further carry a memberselected from the group consisting of metals such as alkali metals,alkaline earth metals, iron, copper, aluminum, gallium, zinc,gadolinium, platinum, vanadium, palladium, titanium, niobium,molybdenum, yttrium, rhenium, neodymium, tungsten, and lanthanum, andcompounds of these metals; and phosphorus compounds, boron compounds andthe like.

As the solid catalysts, zeolites are particularly preferred, andspecific examples thereof include A-type zeolites, L-type zeolites,X-type zeolites, Y-type zeolites, MFI-type zeolites, MWW-type zeolites,β-type zeolites, mordenite, ferrierite, and erionite.

Zeolites of MWW-type MCM-22 and of MFI-type are preferred, and thesezeolites may carry another catalyst. The MFI-type zeolites are zeoliteshaving MFI (Mobil five) structure, and examples thereof include zeoliteshaving MFI structure such as ZSM-5, ZSM-8, zeta 1, zeta 3, Nu-4, Nu-5,TZ-1, TPZ-1, and TS-1. From the viewpoint of high selectivity and goodreaction efficiency, ZSM-5-type zeolites are particularly preferredamong the above examples.

Cations occupying the ion-exchangeable cation sites of zeolite are notparticularly limited, and examples thereof include hydrogen ion(proton); alkali metal ions such as lithium ion, sodium ion, andpotassium ion; alkaline earth metal ions such as magnesium ion, calciumion, strontium ion, and barium ion; transition metal ions such as ironion and silver ion; and primary to quaternary ammonium ions. Inparticular, in terms of achieving high reaction efficiency byenhancement of the surface activity, hydrogen ion (proton) is preferred.The cations may be used alone or as a combination of two or more ofthem.

Although the molar ratio of SiO₂ to Al₂O₃ (SiO₂/Al₂O₃) in thecrystalline structure of zeolite varies depending on the particularreactor, and impurities contained in the materials, the molar ratio ispreferably 5 to 2000, and more preferably 5 to 60. The molar ratios inthese ranges can lead to minimization of further secondary reactions(e.g. alkylation) of the generated phenol. Based on the same reason, thecrystal size of zeolite is preferably (0.001 to 50) μm×(0.01 to 100) μm.The particle size of zeolite is preferably 0.1 to 50 μm, and morepreferably 1 to 20 μm. Also, the nitrogen adsorption specific surfacearea of zeolite is preferably 10 to 1000 m²/g, and more preferably 100to 500 m²/g.

The reaction of phenol and ammonia catalyzed by the catalyst may be agas phase reaction or a liquid-phase reaction. Examples of usablereactors include fixed bed reactors, fluidized bed reactors, and movingbed reactors. The reaction temperature is preferably about 200° C. to600° C. (more preferably 300° C. to 500° C., and still more preferably350° C. to 450° C.). The reaction may be performed at either normal orincreased pressure (preferably at about 5 to 50 atm). Furthermore, themolar ratio of ammonia to phenol is about 1 to 50 (preferably 5 to 30).In the reaction, the reaction system may optionally be diluted withinert gas such as nitrogen, argon, and steam.

Use of the aniline prepared as above contributes to reduction in theamount of petroleum resources used in the production of rubber chemicalsfor a tire such as antioxidants and vulcanization accelerators, andfurthermore it enables production of such rubber chemicals for a tirewithout using petroleum resources.

Examples of the antioxidants include p-phenylenediamine antioxidantssuch as N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine; andquinoline antioxidants such as 2,2,4-trimethyl-1,2-dihydroquinolinepolymers.

For example, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine can beproduced from aniline according to the below-mentioned method. Here,methyl isobutyl ketone to be added to an amine as an intermediate can besynthesized by the following method. Diacetone alcohol, which can besynthesized by, for example, aldol condensation of two molecules of theacetone synthesized by the below-mentioned method, is easily dehydratedto be converted to mesityl oxide. Then, hydrogenation of the mesityloxide with a palladium catalyst or the like gives methyl isobutylketone. According to such a method, antioxidants can be produced withoutusing petroleum resources.

Moreover, 2,2,4-trimethyl-1,2-dihydroquinoline polymers can besynthesized from aniline by feeding acetone any time as needed at atemperature of 140° C. in the presence of an acidic catalyst. Sinceacetone can be produced by the following method, the polymers can beproduced without using petroleum resources.

Acetone required for the synthesis of the antioxidants can besynthesized, for example, as follows: a biomass material is subjected toacetone-butanol fermentation by a microorganism to give a mixed solventof butanol, acetone and the like, and the mixed solvent is distilled sothat acetone is obtained. Examples of the biomass material includecellulose, agricultural products and waste thereof, and sugars, andsugars are particularly preferred. The microorganism for theacetone-butanol fermentation is not particularly limited. Preferredexamples of the microorganism include wild type, variants, orrecombinants of a member selected from the group consisting of thosebelonging to the genus Escherichia, the genus Zymomonas, the genusCandida, the genus Saccharomyces, the genus Pichia, the genusStreptomyces, the genus Bacillus, the genus Lactobacillus, the genusCoryne, or the genus Clostridium. Microorganisms belonging to the genusClostridum are more preferred, and Clostridium acetobutylicum,Clostridium beijerinckii, Clostridium saccharobutylicum, and Clostridiumsaccharoperbutylacetonicum are particularly preferred.

Moreover, microorganisms containing a gene encoding acetoacetatedecarboxylase (EC4.1.1.4), coenzyme A transferase, or thiolase from amicroorganism of the genus Clostridium may be used.

Acetone may also be obtained by dry distillation of wood to givepyroligneous acid, followed by further fractional distillation orseparation by liquid chromatography or the like.

Also, acetone can be synthesized by heating bioethanol at a temperatureof 400° C. or higher in the presence of a Zr—Fe catalyst.

Moreover, acetone can be synthesized through the following steps of:subjecting bioethanol derived from a carbohydrate material to adehydration reaction to synthesize ethylene, synthesizing propylene fromthe ethylene by a general technique in the petrochemical industry, andsubjecting the propylene to a hydration reaction to prepare isopropanol,followed by dehydrogenation.

Furthermore, acetone can be synthesized by pyrolyzing cellulose in awood material to give acetic acid, neutralizing the acetic acid withcalcium hydroxide to give calcium acetate, and then pyrolyzing thecalcium acetate. Since acetic acid is generated by oxidation of ethanolduring the fermentation in the synthesis of bioethanol, the acetic acidcan be utilized to synthesize acetone through the same process as above.

Still furthermore, acetone can be synthesized by subjecting bioethanolderived from a carbohydrate material to a conversion reaction by aZnO/CaO catalyst or the like.

Examples of the vulcanization accelerators include thiazolevulcanization accelerators such as 2-mercaptobenzothiazole anddibenzothiazyl disulfide; and sulfenamide vulcanization acceleratorssuch as N-cyclohexyl-2-benzothiazylsulfenamide,N,N-dicyclohexyl-2-benzothiazylsulfenamide, andN-tert-butyl-2-benzothiazylsulfenamide.

According to the following synthesis method, 2-mercaptobenzothiazole canbe produced from aniline. Here, carbon disulfide can be produced, forexample, by reacting mustard oil contained in an amount of about 0.4% inBrassica juncea, with hydrogen sulfide to separate the carbon disulfide.According to such a method, vulcanization accelerators can be producedwithout using petroleum resources. Moreover, oxidation of thethus-produced 2-mercaptobenzothiazole gives dibenzothiazyl disulfide.

The above-prepared styrene and 1,3-butadiene can be used to produce asynthetic rubber for a tire without using petroleum resources.

Examples of the synthetic rubber for a tire include styrene butadienerubber (SBR), and butadiene rubber (BR). SBR can be produced bycopolymerization of styrene and 1,3-butadiene. BR can be produced bypolymerization of 1,3-butadiene. Here, 1,3-butadiene can be produced,for example, by a method of reacting bioethanol at a high temperature inthe presence of a solid acid catalyst as mentioned above, such aszeolites, alumina, titanium compounds, sulfate ion-supported zirconia,and WO₃-supported zirconia; or a method of oxidizing bioethanol to giveacetaldehyde, followed by addition of bioethanol in the presence of atantalum/silicon dioxide catalyst and then heating. Thus, syntheticrubbers for a tire can be produced without using petroleum resources.

The rubber chemicals for a tire and the synthetic rubbers for a tireobtained as above may be used for rubber compositions for a tire(treads, sidewalls, etc.).

In addition to the above components, the rubber compositionsappropriately contain other compounding ingredients usually used in therubber industry, such as inorganic fillers (e.g. carbon black, silica,clay, aluminum hydroxide, calcium carbonate), silane coupling agents,process oil, softeners, vulcanizing agents, and vulcanizationaccelerating auxiliaries. The rubber compositions may partially containordinary antioxidants, vulcanization accelerators and synthetic rubbers,which are derived from fossil resources such as petroleum.

The rubber compositions may be produced by known methods. For example,the composition can be produced by kneading the components with a rubberkneader such as an open roll mill, a Banbury mixer, and an internalmixer, and vulcanizing the resulting mixture.

The pneumatic tire of the present invention can be produced by a usualmethod using the rubber composition. Specifically, an unvulcanizedrubber composition containing the components as needed is extruded andprocessed into the shape of a tire component, and then subjected tomolding in a usual manner on a tire building machine to form anunvulcanized tire. Thereafter, the unvulcanized tire is subjected toheat and pressure in a vulcanizer to produce a tire.

EXAMPLES

The following description is offered to specifically illustrate thefirst aspect of the present invention based on examples. The firstaspect of the present invention, however, is not limited only to theseexamples.

(Synthesis of Benzene from Alcohol)

Example 1

Ethyl alcohol for industrial use (petroleum-derived ethanol) prepared byhydration of petroleum-derived ethylene was used as an alcohol material.

Benzene was synthesized from the alcohol by using a flow reactor (see,FIG. 1) provided with a gas introduction pipe 1, an alcohol introductionpipe (material introduction pipe) 2, a reaction tube 3 having an alcoholvapor layer (material vapor layer) 4 and a catalyst layer (reactionlayer) 5, a heater (electric furnace) 6 for heating the reaction tube 3,a product trap 7 for collecting a product generated through the catalystlayer 5, and a cooling device 8 a. The product trap 7 was cooled to −15°C. with the cooling device 8 a.

An amount of 10.0 g of a zeolite catalyst H-ZSM-5 (produced by TosohCorporation, 840 HOA, a calcined product of 840 NHA (SiO₂/Al₂O₃=40(molar ratio), nitrogen adsorption specific surface area: 330 m²/g,crystal size: 2 μm×4 μm, particle size: 10 μm)) was placed on a quartzwool provided inside the catalyst layer 5, and nitrogen gas was fed fromthe gas introduction pipe 1. The feed rate of nitrogen gas in terms ofLHSV was set to 1/hr. The reaction tube 3 was warmed by the heater 6 toa predetermined temperature, and then a predetermined amount ofpetroleum-derived ethanol was fed from the alcohol introduction pipe 2.The reaction conditions were as follows: reaction temperature: 500° C.,reaction pressure: normal pressure, feed rate of petroleum-derivedethanol: 1/hr in terms of LHSV, molar ratio of petroleum-derived ethanolto nitrogen (petroleum-derived ethanol/nitrogen): 50/50. The reactiontime was two hours. The resulting product was collected in the producttrap 7 connected to the reaction tube 3.

The product was analyzed by gas chromatography. PORAPAK P (registeredtrademark, produced by GL Sciences Inc.) was used as a column filler foranalysis of the gas component, and SUPELCOWAX (registered trademark,produced by SUPELCO) was used as a column filler for analysis of othercomponents.

The conversion rate of the petroleum-derived ethanol was 100%. Based oncomparison of the number of moles of carbon, the resulting productconsisted of benzene (12.0%), toluene (14.2%), xylene (7.6%), and others(66.2%).

Benzene was recovered by distilling the product. The reflux ratio wasset to 2, and the steam flow rate was set to 0.2 m/s. With the aboveratio of the number of moles produced, the recovery efficiency bydistillation was 90%. Accordingly, the total yield of benzene calculatedfrom the equation below was 11%.Total yield (%)=(number of moles of carbon of benzene produced per unittime)/(number of moles of carbon of ethanol fed per unit time)×recoveryefficiency by distillation×100

Example 2

Benzene was synthesized in the same manner as in Example 1. In thesynthesis, toluene and xylene as by-products were recovered, and wereagain allowed to react in the presence of the zeolite catalyst used inExample 1. The total yield of benzene was 17%.

Example 3

Benzene was synthesized in the same manner as in Example 1, except thatbioethanol was used instead of the petroleum-derived ethanol. Thebioethanol used was derived from corn, and contained about 20% of water,and about 8% of other components such as acetaldehyde. The bioethanolwas used after filtration alone without purification by distillation.The total yield of benzene was 13%.

Example 4

Benzene was synthesized in the same manner as in Example 3, except thata zeolite catalyst H-ZSM-5 (produced by Tosoh Corporation, 820 HOA, acalcined product of 820 NHA (SiO₂/Al₂O₃=23 (molar ratio), nitrogenadsorption specific surface area: 350 m²/g, crystal size: 0.03 μm×0.1μm, particle size: 5 μm)) was used instead of the 840 HOA (produced byTosoh Corporation). The total yield of benzene was 21%.

Example 5

Benzene was synthesized in the same manner as in Example 1, except thata zeolite catalyst H-mordenite (CBV90A (SiO₂/Al₂O₃=90), produced byZeolyst) was used instead of the 840 HOA (produced by TosohCorporation). The total yield of benzene was 1%.

Comparative Example 1

Benzene was synthesized in the same manner as in Example 5, except thatcoal-derived methanol (methanol for industrial use prepared by reactingcarbon monoxide (CO) produced by partial oxidation of coals, withhydrogen under a pressure of 50 to 100 atm at a temperature of 240° C.to 260° C. in the presence of a copper oxide/zinc oxide/aluminacomposite oxide catalyst) was used instead of the petroleum-derivedethanol. The total yield of benzene was 0.5%.

Example 6

Benzene was synthesized from petroleum-derived ethanol by using thezeolite catalyst used in Example 4. The synthesis was performed using asystem (circulation reactor) (see, FIG. 2) including the apparatus shownin FIG. 1 in which the product trap 7 was attached with a heater 8 b, afractionator (fractioning pipe) 9, a distillate trap (target producttrap) 10, and a reactant recirculation lines 12 a and 12 b. In thesystem, a reaction mixture obtained by a catalytic reaction wassubjected to fractional distillation to separate low-boiling products,and then vaporized components and high-boiling products werecontinuously supplied to the reaction tube 3. The product trap 7 washeated with the heater 8 b so that the inside temperature was 90° C.

A reaction was allowed to proceed under the conditions of Example 4using the reactor. The reaction product was continuously distilledthrough the fractioning pipe 9. Subsequently, benzene in the distillatewas solidified and recovered in the distillate trap 10 cooled to −15° C.by a cooling device 11. Gaseous products that had not been solidified orliquefied, and high-boiling products that had not been distilled outwere allowed to be continuously supplied to the reaction tube 3 throughthe reactant recirculation lines 12 a and 12 b.

After feeding petroleum-derived ethanol under the same conditions as inExample 4, the feeding was stopped, and the circulation reaction wasmaintained for 14 hours under the same heating conditions. The totalyield of benzene was 31%.

Example 7

Benzene was synthesized in the same manner as in Example 6, except thatbioethanol was used instead of the petroleum-derived ethanol. The totalyield of benzene was 39%.

(Discussion of Synthesis Examples of Benzene from Alcohol)

Comparison of Example 1 and Example 2 reveals that the yield of benzeneis increased by repetition of the catalytic reaction of the by-products.This is considered to be because toluene and xylene as by-products areconverted to benzene by the catalyst. The results demonstrate anadvantage achieved by repetition of the catalytic reaction step in thisprocess.

Comparison of Example 3 and Example 4 reveals that a difference in theSi/Al ratio (SiO₂/Al₂O₃ ratio) of the zeolite catalyst leads todifferent reactivity and selectivity. However, the reactivity andselectivity supposedly depend also on the reaction temperature andconfiguration of the apparatus. Therefore, optimization of the Si/Alratio according to the reaction apparatus to be used is considerednecessary in some cases.

Example 3 reveals that the use of bioethanol that contains by-productsmainly consisting of water also allows the reaction in the presentinvention to proceed. Comparison of the yields of benzene in Example 1and in Example 3 in terms of the number of moles of carbon whileconsidering the ethanol content shows that the yield in Example 3 inwhich bioethanol was used was slightly higher than the yield in Example1.

Comparison of Examples 1, 2, 4 and 7 reveals that the yield of benzeneis greatly increased by repeatedly bringing the by-products into contactwith the catalyst layer for a plurality of times or in a continuousmanner.

Comparison of the yields of benzene in Example 6 and in Example 7 interms of the number of moles of carbon while considering the ethanolcontent surprisingly shows that the yield of benzene was higher inExample 7 in which bioethanol was used than in Example 6 in whichpetroleum-derived ethanol was used. This is supposedly not only becausethe water contained in bioethanol does not considerably inhibit thereaction, but also because other impurities are converted to benzene, orexhibit their functions to activate the conversion reaction or thecatalyst.

(Synthesis of Benzene from Alcohol via Alkene)

Example 8

An aromatic compound was synthesized from an alcohol via an alkene byusing an apparatus (see, FIG. 3) provided with an alcohol introductionpipe (material introduction pipe) 21, a heater 22 for vaporizing theintroduced alcohol, a dehydration reaction column 23 for dehydrationreaction of the alcohol, a cooling device 24 for cooling the productresulting from the dehydration reaction to recover an alkene, a heater25 for vaporizing the alkene, an aromatic compound synthesis column 26for synthesizing an aromatic compound from the alkene, and a coolingdevice 27 for recovering the generated aromatic compound. Thedehydration reaction column 23 was filled with 10 g of aluminum oxide(101095100, produced by Merck Ltd.) serving as a catalyst, and heated to300° C. The aromatic compound synthesis column 26 had the same structureas that of the reaction tube 3 shown in FIG. 1. Petroleum-derivedethanol was used as a material, and the ethanol was fed to thedehydration reaction column 23 under the same feeding conditions as inExample 1. The resulting ethylene was allowed to react in the aromaticcompound synthesis column 26. The resulting product was distilled andpurified to give benzene in a total yield of 27%.

Example 9

Benzene was synthesized in the same manner as in Example 8, except thatbioethanol was used instead of the petroleum-derived ethanol. The totalyield of benzene was 36%.

Example 10

Benzene was synthesized using an apparatus (see, FIG. 4) having the samestructure as that of the apparatus shown in FIG. 3, except that theapparatus further includes a reactant recirculation line 28 forrecovering by-products generated in the aromatic compound synthesiscolumn 26. Benzene was synthesized by feeding petroleum-derived ethanolunder the same conditions as in Example 8, with the dehydration reactioncolumn 23 and the aromatic compound synthesis column 26 heated to 300°C. and 500° C., respectively. Similarly to Example 6, the circulationreaction time was set to 14 hours. The resulting product was distilledand purified to give benzene. The total yield of benzene was 82%.

Example 11

Benzene was synthesized in the same manner as in Example 10, except thatbioethanol was used instead of the petroleum-derived ethanol. The totalyield of benzene was 90%.

(Synthesis of Aniline from Benzene)

Aniline was synthesized from the benzene obtained by the above method,according to the following method.

Sulfuric acid was added to a chloroform solution containing the benzene.To the solution was then added nitric acid, and the mixture was heatedat a temperature of 50° C. for five hours. After completion of thereaction, the organic layer was neutralized with a 5% aqueous potassiumcarbonate solution, washed with water, and dried on magnesium sulfate.The solvent was evaporated to give a white solid. The white solid wasrecrystallized in petroleum-derived ethanol to give nitrobenzene. Theobtained nitrobenzene was allowed to react with hydrogen gas at atemperature of 200° C. in the presence of a nickel catalyst so thataniline was obtained.

(Method of Preparing Acetone without using Petroleum Resources)

(Method 1-1 of Preparing Acetone without using Petroleum Resources)

A 300-mL fermenter (DASGIP) was filled with 250 mL of a synthesis mediumdescribed by Soni et al. (Soni et al., 1987, Appl. Microbiol.Biotechnol. 27: 1-5), and nitrogen was sparged through the medium for 30minutes. Clostridium acetobutylicum (ATCC824) was inoculated on theresulting medium under anaerobic conditions. The culture temperature wasmaintained at constant 35° C., and the pH was constantly controlled to5.5 with a NH₄OH solution. The anaerobic conditions were maintained andthe shaking speed was maintained at 300 rpm during the fermentationperiod. After five days culture, the culture liquid was distilled andsubjected to separation by a conventionally known ion-exchange resinmethod to give acetone.

(Method 1-2 of Preparing Acetone without using Petroleum Resources)

Acetone was obtained through culture and separation in the same manneras in the above preparation method 1-1, except that the strain IFP903(ATCC39057) was used instead of the strain of Clostridiumacetobutylicum.

(Method 2 of Preparing Acetone without using Petroleum Resources)

Wood chips were placed in an autoclave provided with a smoke-guidingpipe with a cooling pipe, and were heated to 400° C. to collectpyroligneous acid generated. The precipitated tar was removed from theobtained pyroligneous acid, and the resulting pyroligneous acid wasextracted with diethyl ether. The extract was washed with a sodiumhydrogen carbonate solution, and then fractional distillation of thewashed extract was repeated. Thus, acetone was obtained.

Production Example 1 of Antioxidant from Aniline (Method of Synthesis ofAntioxidant TMDQ-1 in Table 1)

To a flask equipped with an acetone introduction device, a distillationdevice, a thermometer, and a stirrer were added 190 g (2.0 mol) of theaniline obtained above (Synthesis of aniline from benzene) andhydrochloric acid (0.20 mol) as an acidic catalyst, and the mixture washeated to 140° C. Subsequently, 580 g (10 mol) of the acetone obtainedabove (Method 1-2 of preparing acetone without using petroleumresources) was continuously fed to the reaction system over 6 hourswhile keeping the temperature at 140° C. Unreacted acetone and anilinethat were distilled out were returned to the reaction system as needed.As a result, 180.7 g (yield: about 30%) of polymers of2,2,4-trimethyl-1,2-dihydroquinoline was obtained. The polymerizationdegree was 2 to 4. Here, unreacted aniline and2,2,4-trimethyl-1,2-dihydroquinoline monomer were recovered byreduced-pressure distillation. The unreacted aniline was distilled outat 140° C. By further heating to 190° C., the monomer was distilled out.The amount and yield of the monomer were 19.1 g and 6.9%, respectively.

Production Example 2 of Antioxidant from Aniline (Method of Synthesis ofAntioxidant 6PPD-1 in Table 1)

Two molecules of the acetone synthesized above (Method 1-2 of preparingacetone without using petroleum resources) were subjected to an aldolcondensation reaction to synthesize diacetone alcohol. The diacetonealcohol was then easily dehydrated to be converted to mesityl oxide. Themesityl oxide was hydrogenated with a palladium catalyst to synthesizemethyl isobutyl ketone.

The following reaction was performed using the biomass-derived anilineobtained by the above method and nitrobenzene generated in that process.Meanwhile, nitrobenzene may be synthesized by oxidation of a part of thebiomass-derived aniline according to a known method.

An amount of 187 g of a 25% aqueous tetramethylammonium hydroxidesolution (TMAOH) was concentrated by distillation at a temperature of55° C. under a pressure of 75 mbar to give a 35% solution. Afteraddition of the biomass-derived aniline (269 mL) to the solution, theaniline/water azeotrope was evaporated at a temperature of 75° C. undera pressure of 75 mbar until the molar ratio of water/base reached about4:1. Subsequently, 60 g of the nitrobenzene was added and the resultingmixed solution was further stirred for four hours, while distillation ofthe water/aniline azeotrope was continued. To the crude mixed solutionwere added 2.2 g of a Pt/C catalyst (5% Pt) and 120 mL of water. Next,at a temperature of 80° C., the pressure was increased to the maximum of15 bar with hydrogen, and then the reaction mixture was stirred until nofurther absorption of hydrogen was found. To the resulting mixture wasadded 100 mL of toluene, and the catalyst was removed by filtration,followed by separation of the mixture into an organic phase and a waterphase with a separatory funnel. Then, purification of the organic phaseby fractional distillation gave 4-aminodiphenylamine in a yield of 91%.

An amount of 129.3 g of the 4-aminodiphenylamine, 120.2 g of methylisobutyl ketone synthesized above, 0.77 g of a platinum catalyst (5% Pton carbon sulfide powder (hydrous product), water content: 55.26% bymass, produced by N.E. Chemcat Corporation), and 0.65 g of activatedcarbon (Taiko activated carbon S-type, produced by Futamura ChemicalCo., Ltd.) were introduced into a stirring autoclave and exposed to ahydrogen atmosphere. Then, the inside temperature of the autoclave wasraised from room temperature to 150° C. over about one hour.Subsequently, the hydrogen pressure was increased to 30 kgf/cm² (2.94MPa), and a reaction was allowed to proceed at the same temperature andthe same pressure while feeding the consumed amount of hydrogen.

After two hours from the start of increasing the hydrogen pressure,hydrogen was released from the autoclave to decrease the pressure tonormal pressure, while the reaction solution was cooled to roomtemperature. The reaction solution was filtrated to remove the catalystand the activated carbon. The resulting reaction product was subjectedto separation by high performance liquid chromatography to give4-(1,3-dimethylbutylamino)diphenylamine (antioxidant 6PPD-1) in a yieldof 99.4%.

(Method of Preparing Carbon Disulfide without using Petroleum Resources)

Carbon disulfide was obtained by reacting mustard oil contained in anamount of about 0.4% in Brassica juncea, with hydrogen sulfide, or byheating charcoal and sulfur at a temperature of 900° C.

Production Example 1 of Vulcanization Accelerator MBT from Aniline(Method of Synthesis of Vulcanization Accelerator MBT-1 in Table 1)

An amount of 93 g (1.0 mol) of the aniline obtained in the aboveProduction Example, 80 g (1.1 mol) of the carbon disulfide obtainedabove (Method of preparing carbon disulfide without using petroleumresources), and 16 g (1.0 mol) of sulfur were introduced into a 300-mLpressurized reactor, and subjected to a reaction for two hours at atemperature of 250° C. under a pressure of 10 MPa, followed by coolingto 180° C. Thus, a crude product of 2-mercaptobenzothiazole was obtainedin an amount of 130 g (yield: 87%). Moreover, the obtained crude productof 2-mercaptobenzothiazole (purity: 79%) was dissolved in isopropanol atthe boiling temperature in an inert gas atmosphere of nitrogen. Theresulting mixture was left at room temperature to cool. A precipitatedproduct was separated by filtration, washed with isopropanol, and dried.Thus, a light yellow product (2-mercaptobenzothiazole with high purity(melting point: 180.1° C. to 181.1° C., purity: 98.1%)) was obtained.

Production Example 1 of Vulcanization Accelerator CBS from Aniline(Method of Synthesis of Vulcanization Accelerator CBS-1 in Table 1)

The crude product of 2-mercaptobenzothiazole obtained above wasdissolved in an aqueous sodium hydroxide solution to prepare a 20%aqueous solution of a sodium salt of mercaptobenzothiazole. To thesolution was added an equivalent molar amount of cyclohexylamine. Themixed solution was further mixed with 100 mL of methanol at atemperature of 40° C. A 13% solution of sodium hypochlorite was allowedto act on the resulting mixture, in an amount of 1.2 times the molaramount of the sodium salt of mercaptobenzothiazole, followed by stirringfor one hour. After the reaction, water and the organic solvent wereremoved so that an oil of N-cyclohexyl-benzothiazolylsulfenamide wasobtained (yield: 93%).

(Synthesis of Styrene from Benzene)

Benzene was allowed to react with the ethylene obtained by a dehydrationreaction of bioethanol in Example 9 or 11, in the presence of aluminumchloride under the following conditions: reaction temperature of 320° C.and benzene/ethylene (molar ratio) of 10 to give ethylbenzene. Theobtained ethylbenzene was dehydrogenized in the presence of an ironcatalyst to give styrene.

(Method of Preparing 1,3-Butadiene without using Petroleum Resources)

Bioethanol was oxidized to be converted to acetaldehyde, and thenbioethanol was added thereto and heated in the presence of atantalum/silicon dioxide catalyst to give 1,3-butadiene. Alternatively,1,3-butadiene can be obtained in a small amount in the case wherebioethanol is subjected to a dehydration reaction in Example 9 or 11.Thus, this 1,3-butadiene, after separation, may also be used.

(Synthesis of SBR)

Using the styrene and 1,3-butadiene obtained in the above synthesisexamples, SBR was polymerized according to the method below.

(Synthesis Example of Solution Polymerized SBR (Method of Synthesis ofS-SBR-1 in Table 1))

The inside of a stainless steel polymerization reactor having aninternal volume of 20 L was washed and dried, and then the inside airwas replaced with dry nitrogen. Hexane (10.2 kg, specific gravity: 0.68g/cm³), the 1,3-butadiene (547 g) obtained above (Method of preparing1-3 butadiene without using petroleum resources), the styrene (173 g)obtained above (Synthesis of styrene from benzene), tetrahydrofuran (6.1mL), and ethylene glycol diethyl ether (5.0 mL) were introduced into thepolymerization reactor. Subsequently, n-butyllithium (13.1 mmol) wasintroduced as an n-hexane solution to start polymerization.

The 1,3-butadiene was copolymerized with the styrene for three hours ata stirring rate of 130 rpm and at a temperature inside thepolymerization reactor of 65° C. while continuously feeding the monomersinto the polymerization reactor. During the whole polymerizationprocess, 821 g of 1,3-butadiene and 259 g of styrene were fed.

Next, 20 mL of a hexane solution containing 0.54 mL of methanol wasadded to the polymer solution, and the resulting polymer solution wasfurther stirred for five minutes.

To the polymer solution was added 13.1 mmol of3-(N,N-dimethylaminopropyl)-trimethoxysilane (produced by AZmax). Then,a solution-polymerized SBR (S-SBR-1) was recovered from the polymersolution by steam stripping.

(Synthesis Example of Emulsion Polymerized SBR (Method of Synthesis ofE-SBR-1 in Table 1))

Water (2000 g), a rosin acid soap (45 g, produced by Harima Chemicals,Inc.), a fatty acid soap (1.5 g, produced by Wako Pure ChemicalIndustries, Ltd.), sodium phosphate (8 g, produced by Wako Pure ChemicalIndustries, Ltd.), the styrene (250 g) obtained above (Synthesis ofstyrene from benzene), the 1,3-butadiene (750 g) obtained above (Methodof preparing 1-3 butadiene without using petroleum resources), andtert-dodecyl mercaptan (2 g, produced by Wako Pure Chemical Industries,Ltd.) were charged in a pressure-resistant reactor equipped with astirrer. The temperature of the reactor was set to 5° C. To the reactorwere added an aqueous solution containing para-menthane hydroperoxide (1g, produced by NOF corporation) and sodium formaldehyde sulfoxylate (1.5g, produced by Wako Pure Chemical Industries, Ltd.), and an aqueoussolution containing sodium ethylenediaminetetraacetate (0.7 g, producedby Wako Pure Chemical Industries, Ltd.) and ferric sulfate (0.5 g,produced by Wako Pure Chemical Industries, Ltd.) to startpolymerization. After five hours from the start of polymerization,N,N′-dimethyldithiocarbamate (2 g, produced by Wako Pure ChemicalIndustries, Ltd.) was added to stop the reaction. Thus, a latex wasobtained.

Unreacted monomers were removed from the obtained latex by steamdistillation. Thereafter, the resulting latex was added to an alcohol,and adjusted to the pH of 3 to 5 with a saturated aqueous sodiumchloride solution or formic acid for coagulation to give a polymercrumb. The polymer was dried in a vacuum oven at a temperature of 40° C.so that a solid rubber (emulsion-polymerized SBR (E-SBR-1)) wasobtained.

(Synthesis Example of BR)

(Method of Synthesis of BR-1 in Table 1)

The 1,3-butadiene obtained above (Method of preparing 1,3-butadienewithout using petroleum resources) was used to polymerize BR (BR-1 inTable 1) according to the following method.

The air inside a reactor (3 L-pressure-resistant stainless steel vessel)was replaced with nitrogen. While maintaining the nitrogen atmosphere,1800 mL of cyclohexane, 150 g of the 1,3-butadiene obtained above(Method of preparing 1,3-butadiene without using petroleum resources),and 1.5 mL of THF (tetrahydrofuran) were introduced into the vessel, andstirring was started. Next, the temperature inside the vessel was raisedto 40° C., and 1 mL of a butyllithium solution was introduced thereintoto start polymerization. After stirring for three hours, 1 mL of asilane solution (1) (a mixed solution ofbis(dimethylamino)methylvinylsilane (3 mL) and anhydrous cyclohexane(7.5 mL), produced by Shin-Etsu Chemical Co., Ltd.), and 1.49 mmol ofbis(dimethylamino)methylvinylsilane were added and stirred for 15minutes. An amount of 0.5 mL of IPA (isopropyl alcohol) and 1 mL of aBHT (3,5-dibutyl-4-hydroxytoluene) solution were added to the polymersolution, and further stirred for five minutes. Next, the resultingpolymer solution was added to 3 L of methanol to obtain a coagulatedpolymer, followed by overnight air-drying and then 24-hour drying underreduced pressure. Thus, a polymer (BR-1 in Table 1) was obtained in ayield of 96%. An analysis found that the obtained polymer had an Mw of26.2×10⁴, and Mw/Mn of 1.29. The polymer had a vinyl bond content of11.4 mol % of the conjugated diene unit content (100 mol %).

In this polymer, the content of structural units represented by thefollowing formula (I) calculated from the introduction amount was 0.01mmol per g of the polymer. The content of conjugated diene structuralunits in the diene copolymer was 98.4% by mass.

(in the formula, X¹, X², and X³ each independently represent a grouprepresented by the following formula (Ia), a hydroxyl group, ahydrocarbyl group, or a substituted hydrocarbyl group, and at least oneof X¹, X², and X³ is a group represented by the formula (Ia) or ahydroxyl group.)

(in the formula, R¹ and R² each independently represent a C1-C6hydrocarbyl group, a C1-C6 substituted hydrocarbyl group, a silyl group,or a substituted silyl group, and R¹ and R² may be bound together toform a ring structure with the nitrogen atom.)

(Method of Synthesis of BR-2 in Table 1)

For comparison, an ordinary fossil resource-derived 1,3-butadiene wasused to polymerize BR (BR-2 in Table 1) according to the followingmethod.

The air inside a reactor (3 L-pressure-resistant stainless steel vessel)was replaced with nitrogen. While maintaining the nitrogen atmosphere,1800 mL of cyclohexane, 150 g of fossil resource-derived 1,3-butadiene(produced by Takachiho Chemical Industrial Co., Ltd.), and 1.5 mL of THFwere introduced into the vessel, and stirring was started. Next, thetemperature inside the vessel was raised to 40° C., and 1 mL of abutyllithium solution was introduced thereinto to start polymerization.After stirring for three hours, 1 mL of the silane solution (1) and 1.49mmol of bis(dimethylamino)methylvinylsilane were added and stirred for15 minutes. An amount of 0.5 mL of IPA and 1 mL of a BHT solution wereadded to the polymer solution, and further stirred for five minutes. Theresulting polymer solution was added to 3 L of methanol to obtain acoagulated polymer, followed by overnight air-drying and then 24-hourdrying under reduced pressure. Thus, a polymer (BR-2 in Table 1) wasobtained in a yield of 96%. An analysis found that the obtained polymerhad an Mw of 26.1×10⁴, and Mw/Mn of 1.30. The polymer had a vinyl bondcontent of 11.3 mol % of the conjugated diene unit content (100 mol %).

In this polymer, the content of structural units represented by theformula (I) calculated from the introduction amount was 0.01 mmol per gof the polymer. The content of conjugated diene structural units in thediene copolymer was 98.4% by mass.

(Preparation of Rubber Composition for Tread)

Chemical agents each in an amount shown in Process 1 in Table 1 wereintroduced into a Banbury mixer and kneaded for five minutes to raisethe outlet temperature to about 150° C. Thereafter, sulfur andvulcanization accelerators each in an amount shown in Process 2 wereadded to the kneaded mixture obtained in Process 1, and then kneadedwith the Banbury mixer for about three minutes to adjust the outlettemperature to 100° C. Thus, an unvulcanized rubber composition wasobtained. The resulting unvulcanized rubber composition was molded intoa tread shape, assembled with other tire components and then vulcanizedfor 20 minutes at a temperature of 170° C. Thus, a test tire wasproduced.

Furthermore, each unvulcanized rubber composition was vulcanized for 20minutes at a temperature of 170° C. to prepare a vulcanized rubbersheet.

The chemical agents used above were as follows.

-   S-SBR-1: synthesized by the above method (terminally modified with a    compound represented by the following formula (II), bound styrene    content: 25% by mass, vinyl content: 59% by mass)

(in the formula, R³, R⁴, R⁵═—OCH₃; R⁶, R⁷═—CH₃; and n=3)

-   S-SBR-2: SE0190, produced by Sumitomo Chemical Co., Ltd.,    (terminally modified with a compound represented by the above    formula (II), bound styrene content: 25% by mass, vinyl content: 59%    by mass)-   E-SBR-1: synthesized by the above method-   E-SBR-2: SBR1502, produced by JSR Corporation-   BR-1: synthesized by the above method-   BR-2: synthesized by the above method-   NR: RSS #3-   Silica: Ultrasil VN2 (BET specific surface area: 125 m²/g), produced    by Degussa-   Carbon black: Niteron #55S (carbon black made from coal-derived    heavy oil, N₂SA: 28×10³ m²/kg), produced by Nippon Steel Chemical    Carbon Co., Ltd.-   Silane coupling agent: Si69, produced by Degussa-   Mineral oil: PS-32, produced by Idemitsu Kosan Co., Ltd.-   Stearic acid: Kiri, produced by NOF Corporation-   Zinc oxide: zinc oxide #2, produced by Mitsui Mining & Smelting Co.,    Ltd.-   Antioxidant 6PPD-1: synthesized by the above method-   Antioxidant 6PPD-2: Nocrac 6C, produced by Ouchi Shinko Chemical    Industrial Co., Ltd.-   Antioxidant TMDQ-1: synthesized by the above method-   Antioxidant TMDQ-2: Nocrac 224, produced by Ouchi Shinko Chemical    Industrial Co., Ltd.-   Wax: SUNNOC Wax, produced by Ouchi Shinko Chemical Industrial Co.,    Ltd.-   Sulfur: sulfur powder, produced by Tsurumi Chemical Industry Co.,    Ltd.-   Vulcanization accelerator CBS-1: synthesized by the above method-   Vulcanization accelerator CBS-2: Nocceler CZ, produced by Ouchi    Shinko Chemical Industrial Co., Ltd.-   Vulcanization accelerator MBT-1: synthesized by the above method-   Vulcanization accelerator MBT-2: Nocceler M, produced by Ouchi    Shinko Chemical Industrial Co., Ltd.

The following evaluations were made using the thus obtained unvulcanizedrubber compositions, vulcanized rubber sheets, and test tires. Table 1shows the test results.

(Vulcanization Test)

The unvulcanized rubber composition was exposed to a low amplitude (1°in the test) sinusoidal vibration which did not break the composition,by using a W-type curelastometer (produced by JSR Corporation) accordingto “Die vulcanization test method A” of “Vulcanization test withoscillating curemeters” in JIS K 6300-2. The torque transferred from thetest sample to the upper die was measured during the transition fromunvulcanized state to over-vulcanized state so that a vulcanizationcurve of the unvulcanized rubber composition at a temperature of 170° C.was obtained.

(1) Torque Rise

The torque rise was calculated by subtracting the minimum torque (ML)from the maximum torque (MH). The torque rise of each composition wasshown as an index relative to the torque rise of the referencecomposition (Comparative Example) regarded as 100. The index was used asbarometer of crosslinking efficiency. A larger index which indicateshigher crosslinking efficiency is favorable.

(2) Cure Time

The tc (95) (95% torque rise point: t95) (min) serving as an indicatorof the optimum cure time was calculated. Similarly to the item (1), thetc of each composition was shown as an index relative to the tc of thereference composition (Comparative Example) regarded as 100. A smallerindex indicates a higher curing rate.

(Breaking Energy Index)

According to JIS K 6251 “Rubber, vulcanized orthermoplastic—Determination of tensile stress-strain properties”, thetensile strength and elongation at break of each vulcanized rubber sheetwere measured. The breaking energy was then calculated from the formula:(tensile strength×elongation at break)/2, and furthermore the breakingenergy index was calculated from the equation below. A larger breakingenergy index indicates better mechanical strength.(Breaking energy index)=(Breaking energy of each composition)/(Breakingenergy of reference composition (Comparative Example))×100

(Abrasion Resistance Test (Abrasion Test))

The produced set of test tires were mounted on a car, and the decreasein the depth of tire grooves after the car had run 8000 km in an urbanarea was measured. The running distance that decreased the depth of tiregrooves by 1 mm was calculated. Further, based on the followingequation, the decrease in the depth of tire grooves for each compositionwas expressed as an abrasion resistance index relative to the abrasionresistance index of a reference comparative example regarded as 100. Alarger abrasion resistance index indicates better abrasion resistance.(Abrasion resistance index)=(Running distance that decreased the groovedepth by 1 mm for each composition)/(Running distance that decreased thegroove depth by 1 mm for reference composition (ComparativeExample))×100

(Rolling Resistance Test)

A vulcanized rubber sheet having a size of 2 mm×130 mm×130 mm wasprepared, and a test sample was cut out from the vulcanized rubbersheet. The tan δ of the test sample of each composition was measuredusing a viscoelastic spectrometer VES (produced by Iwamoto SeisakushoCo., Ltd.) under the following conditions: temperature of 50° C.;initial strain of 10%; dynamic strain of 2%; and frequency of 10 Hz.Based on the equation below, the rolling resistance property wasexpressed as a rolling resistance index relative to the rollingresistance index of a reference comparative example regarded as 100. Asmaller index indicates lower rolling resistance and better fueleconomy.(Rolling resistance index)=(tan δ of each composition)/(tan δ ofreference composition (Comparative Example))×100

(Wet Grip Performance)

The grip performance was evaluated based on the braking performanceresults obtained by the anti-lock braking system (ABS) evaluation test.More specifically, the produced set of test tires were mounted on a 1800cc-class passenger car equipped with ABS, and the car was driven on anasphalt road surface (road surface condition: wet, skid number: about50). Then, the brake was stepped on when the speed was 100 km/h, and thedeceleration until the car stopped was calculated. The decelerationherein refers to a distance required for the passenger car to stop.

Further, based on the following equation, the deceleration for the tiresof each composition was expressed as a wet grip performance indexrelative to the wet grip performance index of the reference composition(Comparative Example) regarded as 100. A larger wet grip performanceindex indicates better braking performance and therefore better wet gripperformance.(Wet grip performance index)=(Deceleration for reference composition(Comparative Example))/(Deceleration for each composition)×100

(Dry Grip Performance)

The produced set of test tires were mounted on a passenger car, and thecar was driven on a dry asphalt road surface in a test course. Theproperties of the tires including steering response, rigidity and gripwere evaluated based on sensory evaluation by a driver. The results wereexpressed as an index relative to the results of the referencecomposition (Comparative Example) regarded as 100. A larger indexindicates better performance with better dry grip performance andhandling stability.

TABLE 1 Comparative Example Example Composition Process 1 S-SBR-1 30(parts by mass) S-SBR-2 30 E-SBR-1 20 E-SBR-2 20 BR-1 30 BR-2 30 NR 2020 Silica 75 75 Carbon black 5 5 Silane coupling agent 6 6 Mineral oil10 10 Stearic acid 2 2 Zinc oxide 3 3 Antioxidant 6PPD-1 1.5 Antioxidant6PPD-2 1.5 Antioxidant TMDQ-1 0.5 Antioxidant TMDQ-2 0.5 Wax 1.5 1.5Process 2 Sulfur 1.5 1.5 Vulcanization accelerator CBS-1 1.5Vulcanization accelerator CBS-2 1.5 Vulcanization accelerator MBT-1 0.2Vulcanization accelerator MBT-2 0.2 Evaluations Torque rise 101 100 Curetime 99 100 Breaking energy index 100 100 Abrasion resistnace index 101100 Rolling resistance index 99 100 Wet grip performance index 101 100Dry grip performance index 100 100

The rubber properties including vulcanization properties and breakingenergy index, and the tire properties including abrasion resistance,rolling resistance property, and wet/dry grip performance in Examplewere all equal to those in Comparative Example in which conventionalvulcanization accelerators, antioxidants, and various synthetic rubbersthat were synthesized from fossil resources were used. This demonstratedthat the Example makes it possible to cope with depletion of fossilresources without any practical problems.

The following description is offered to specifically illustrate thesecond aspect of the present invention based on examples. The secondaspect of the present invention, however, is not limited only to theseexamples.

(Synthesis 1 of Phenol from Biomass Material (using Microorganism))

(Preparation of Transformant)

A tpl gene was amplified from genomic DNA of Pantoea agglomerans AJ2985as a template DNA with primers 5′-GCGGTACCATGAACTATCCTGCCGAGCC-3′(forward) (SEQ ID NO: 1) and 5′-GCGGCCGCTTAAATAAAGTCAAAACGCGC-3′(reverse) (SEQ ID NO: 2) by PCR. The primers herein were designed tocontain the sequences GGTACC and CGGCCG, respectively, corresponding torestriction enzymes KpnI and NotI, respectively, based on the sequenceof the tpl gene listed in GenBank under accession No. D13714. Theamplified tpl gene was confirmed to have no problem in its sequence by aknown method.

The amplified tpl gene was incorporated into a plasmid pTn-1, whichcontained a salicylate-inducible NagR/pNagAa promoter and had ampicillinresistance and gentamicin resistance, by using the restriction enzymesKpnI and NotI, so that pNW1 was obtained.

Next, the obtained pNW1 was incorporated into Pseudomonas putida S12(ATCC700801), an organic solvent tolerant bacterium, by a known method,so that a transformant was obtained.

(Semi-Batch Culture)

Next, the obtained transformant was cultured under the followingconditions to biosynthesize phenol from glucose. A BioFlo IIc fermentor(produced by New Brunswick Scientific) having an internal volume of 2.5L was used for the culture. During the culture, oxygen was fed to aheadspace of the fermentor at a rate of 300 mL/min, and the fed oxygenwas mixed into the medium by rotating an impeller at the bottom of thefennentor. During the culture, the pH was maintained at 7.0 using 4 MKOH. Furthermore, the dissolved oxygen tension was maintained at about20% saturation by controlling the rotation rate of the impeller. Theinitial amount of the culture liquid at the start of culture was set to1.5 L. The absorbance at 600 nm (OD₆₀₀) of the culture liquid wasperiodically measured. Feeding of a feed liquid was started when no morechange was observed in the OD₆₀₀. The feed rate of the feed liquid wasset to 4 mL/h when the cell dry weight (CDW) was less than 3 g/L, 9 mL/hwhen the CDW was 3 to 4.5 g/L, and 20 mL/h when the CDW exceeded 4.5g/L. The culture was performed at a temperature of 30° C.

The medium composition at the start of culture, and the composition ofthe feed liquid are as follows.

<Medium Composition at the Start of Culture (The Following Amounts arePer Liter.)>

30 mmol K₂HPO₄, 20.5 mmol NaH₂PO₄, 25 mmol D-glucose, 15 mmol NH₄Cl, 1.4mmol Na₂SO₄, 1.5 mmol MgCl₂, 0.5 g yeast extract, 10 ml trace solution1, 10 mg gentamicin, 0.1 mmol salicylic acid

<Composition of Feed Liquid (The Following Amounts are Per Liter.)>

750 mmol D-glucose, 225 mmol NH₄Cl, 21 mmol Na₂SO₄, 7.4 mmol MgCl₂, 13mmol CaCl₂, 0.5 g yeast extract, 100 ml trace solution 2, 10 mggentamicin, 1 mmol salicylic acid

<Composition of Trace Solution 1 (The Following Amounts are Per Liter.)>

4 g EDTA, 0.2 g ZnSO₄.7H₂O, 0.1 g CaCl₂.2H₂O, 1.5 g FeSO₄.7H₂O, 0.02 gNa₂MoO₄.2H₂O, 0.2 g CuSO₄.5H₂O, 0.04 g CoCl₂.6H₂O, 0.1 g MnCl₂.4H₂O

<Composition of Trace Solution 2 (The Following Amounts are Per Liter.)>

4 g EDTA, 0.2 g ZnSO₄.7H₂O, 0.1 g CaCl₂.2H₂O, 6.5 g FeSO₄.7H₂O, 0.02 gNa₂MoO₄.2H₂O, 0.2 g CuSO₄.5H₂O, 0.04 g CoCl₂.6H₂O, 0.1 g MnCl₂.4H₂O,0.024 g H₃BO₃, 0.02 g NiCl.6H₂O

After 25 hours culture, diethyl ether was added to the culture liquid,followed by two times of extraction. The resulting crude extract wasconcentrated by an evaporator, and then purified by flash chromatographywith a column filled with silica gel 60 to give phenol. The phenol wasidentified by NMR and IR.

(Synthesis 2-1 of Phenol from Biomass Material (using Catalyst))

Copper acetate and NH₄-ZSM-5 (produced by Tosoh Corporation, 820 NHA,SiO₂/Al₂O₃=23 (molar ratio), nitrogen adsorption specific surface area:350 m²/g, crystal size: 0.03 μm×0.1 μm, particle size: 5 μm) were usedas starting materials to prepare a ZSM-5 catalyst carrying Cu. Ammoniawater was added to an aqueous copper acetate solution to adjust the pHto 11 so that copper ions in the solution formed a copper ammine complex[Cu(NH₃)₄]²⁺. To the resulting solution was added NH₄-ZSM-5. The mixturewas stirred for 24 hours with heating at 60° C. so that the NH₄-ZSM-5was subjected to ion exchange with copper ions, followed by filtration,washing, and drying at 100° C. for 24 hours. The dried product wascalcined at 500° C. for one hour under air flow of 1 L/min to give acatalyst. The amount of copper carried by the prepared catalyst wascontrolled by changing the concentration of the solution used for ionexchange. As a result of an atomic absorption spectroscopy assay, theamount of Cu carried by the prepared catalyst was Cu/Al=0.13 to 1.67(Cu: 0.54 to 6.83 wt %).

Two quartz tubes each having an inner diameter of 32 mm were connectedto each other. The tubes were packed with 10.0 g of a zeolite catalystH-ZSM-5 (produced by Tosoh Corporation, 820 HOA, a calcined product of820 NHA (SiO₂/Al₂O₃=23)) and 10.0 g of the Cu/ZSM-5 synthesized by theabove method, respectively, on quartz wool in the central region of eachtube. Nitrogen gas was fed from the catalyst column not carrying Cu. Thefeed rate of nitrogen gas in terms of LHSV was set to 1/hr. The quartstubes were placed in an electric furnace, and the temperature was raisedto a predetermined temperature. Thereafter, a predetermined amount ofbioethanol (produced by BRAZIL-JAPAN ETHANOL Co., Ltd.) purified bydistillation was fed. Here, the reaction conditions were as follows:reaction temperature: 450° C., reaction pressure: normal pressure, feedrate of bioethanol in terms of LHSV: 1/hr, molar ratio of bioethanol tonitrogen (bioethanol/nitrogen): 50/50.

A reaction mixture obtained through continuous feeding of bioethanol wasdistilled, followed by separation by high performance liquidchromatography. Thus, 5 g of pure phenol was obtained.

(Synthesis 2-2 of Phenol from Biomass Material)

An amount of 20 g of phenol was obtained in the same manner as inSynthesis 2-1, except that Re/ZSM-5 modified to carrymethyltrioxorhenium by the CVD method was used instead of the Cu/ZSM-5.

(Synthesis 2-3 of Phenol from Biomass Material)

An amount of 0.1642 g (627 μmol) of titanyl bis(acetylacetonate)(TiO(acac)₂) was dissolved in 40 mL of methylene chloride. To thesolution was added 0.950 g of H-ZSM-5 (produced by Tosoh Corporation,840 HOA, a calcined product of 840 NHA (SiO₂/Al₂O₃=40 (molar ratio),nitrogen adsorption specific surface area: 330 m²/g, crystal size: 2μm×4 μm, particle size: 10 μm)), and the mixture was stirred underheating at a temperature of 40° C. to remove methylene chloride. Aftersufficient drying, the dried product was calcined in a muffle furnaceunder air flow at a temperature of 150° C. for two hours and then at atemperature of 600° C. for four hours. Thus, 1.00 g of a catalyst(TiOx/H-ZSM-5) was prepared. The amount of titanium carried by theprepared catalyst in terms of titanium oxide (TiO₂) was 5.0% by mass.

An amount of 8 g of phenol was then obtained in the same manner as inthe synthesis example 2-1, except that the TiOx/H-ZSM-5 obtained by theabove method was used instead of the Cu/ZSM-5, and hydrogen/oxygen(pressure ratio: 1/20) was used instead of nitrogen.

Production Example 1 of Aniline from Phenol

Zeolite β (produced by PQ Corporation, CP811BL-25, silica/alumina ratio:12.5 (molar ratio), nitrogen adsorption specific surface area: 750 m²/g)was used as a catalyst. First, a reaction tube was filled with 0.65 g ofthe zeolite β. Nitrogen and ammonia gas at a volume ratio of 50:16.6were allowed to flow through the tube, while the tube was heated in anelectric furnace to a predetermined temperature, and then apredetermined amount of phenol was fed by a pump. Here, the reactionconditions were as follows: reaction temperature: 450° C., reactionpressure: normal pressure, feed rate of phenol in terms of LHSV:1.29/hr, molar feed ratio of ammonia to phenol: 9. After four hours fromthe start of reaction, a steady state was achieved. Thereafter, agas-liquid separator was placed at an exit of the reaction tube tocollect the resulting reaction liquid. An analysis of the product foundthat aniline was obtained in a yield of 21.2%. The analysis wasperformed by gas chromatography (columns: FFAP and CP-WAX). The yieldwas calculated from the following equation.Yield (%)=(number of moles of aniline produced per unit time)/(number ofmoles of phenol fed per unit time)×100

Production Example 2 of Aniline from Phenol

Aniline was obtained in a yield of 84.3% by performing a reaction in thesame manner as in Production Example 1, except that the catalyst inProduction Example 1 was changed to H-ZSM-5 (produced by TosohCorporation, 820 HOA, a calcined product of 820 NHA (SiO₂/Al₂O₃=23(molar ratio), nitrogen adsorption specific surface area: 350 m²/g,crystal size: 0.03 μm×0.1 μm, particle size: 5 μm)), the reactiontemperature was changed to 500° C., the pressure was changed to 537 KPa,and the reaction time was changed to eight hours.

Production Example 3 of Aniline from Phenol

Aniline was obtained in a yield of 15.2% by performing a reaction in thesame manner as in Production Example 1, except that the ammonia inProduction Example 1 was changed to monomethylamine, and the pressurewas changed to 2859 KPa.

Production Example 4 of Aniline from Phenol

An alumina catalyst was prepared by mixing a mixture consisting ofbayerite (Versal B, produced by LaRoche Chemical) and pseudoboehmite(Versal 900, produced by LaRoche Chemical) at a mass ratio of 4:1 with a0.4 M aqueous nitric acid solution, and then heating the resultingmixture in a muffle furnace at a temperature of 500° C. for eight hours.Aniline was then obtained in a yield of 46.3% by performing a reactionin the same manner as in Production Example 1, except that the obtainedalumina catalyst was used instead, the reaction temperature was changedto 365° C., and the pressure was changed to 1.7 MPa.

Production Example 3 of Antioxidant from Aniline (Method of Synthesis ofAntioxidant TMDQ-3 in Table 2)

To a flask equipped with an acetone introduction device, a distillationdevice, a thermometer, and a stirrer were added 190 g (2.0 mol) of theaniline obtained above (Synthesis 1 of phenol from biomass material(using microorganism) and Production Example 2 of aniline from phenol)and hydrochloric acid (0.20 mol) as an acidic catalyst, and the mixturewas heated to 140° C. Subsequently, 580 g (10 mol) of the acetoneobtained above (Method 1-1 of preparing acetone without using petroleumresources) was continuously fed to the reaction system over 6 hourswhile keeping the temperature at 140° C. Unreacted acetone and anilinethat were distilled out were returned to the reaction system as needed.As a result, 180.7 g (yield: about 30%) of polymers of2,2,4-trimethyl-1,2-dihydroquinoline was obtained. The polymerizationdegree was 2 to 4. Here, unreacted aniline and2,2,4-trimethyl-1,2-dihydroquinoline monomer were recovered byreduced-pressure distillation. The unreacted aniline was distilled outat 140° C. By further heating to 190° C., the monomer was distilled out.The amount and yield of the monomer were 19.1 g and 6.9%, respectively.

According to the present method, phenol was synthesized by biosynthesisfrom a biomass material, and aniline was then highly efficientlysynthesized from the thus obtained phenol by using a catalyst. Thus,aniline could be efficiently synthesized while suppressing the totalenergy consumption and CO₂ emission. Furthermore, the combined use ofthe acetone produced by biosynthesis made it possible to highlyefficiently synthesize an antioxidant in an environmentally friendlymanner.

Production Example 4 of Antioxidant from Aniline (Method of Synthesis ofAntioxidant 6PPD-3 in Table 2)

Two molecules of the acetone synthesized above (Method 1-1 of preparingacetone without using petroleum resources) were subjected to an aldolcondensation reaction to synthesize diacetone alcohol. The diacetonealcohol was then easily dehydrated to be converted to mesityl oxide. Themesityl oxide was hydrogenated with a palladium catalyst to synthesizemethyl isobutyl ketone.

Aniline was also obtained in the same manner as mentioned aboveaccording to (Synthesis 1 of phenol from biomass material (usingmicroorganism)) and (Production Example 2 of aniline from phenol).

An antioxidant 6PPD was synthesized from the obtained aniline,nitrobenzene obtained by oxidation of the aniline by a known method, andthe obtained methyl isobutyl ketone by the following method.

An amount of 187 g of a 25% aqueous tetramethylammonium hydroxidesolution (TMAOH) was concentrated by distillation at a temperature of55° C. under a pressure of 75 mbar to give a 35% solution. Afteraddition of the biomass-derived aniline (269 mL) to the solution, theaniline/water azeotrope was evaporated at a temperature of 75° C. undera pressure of 75 mbar until the molar ratio of water/base reached about4:1. Subsequently, 60 g of the nitrobenzene was added and the resultingmixed solution was further stirred for four hours, while distillation ofthe water/aniline azeotrope was continued. To the crude mixed solutionwere added 2.2 g of a Pt/C catalyst (5% Pt) and 120 mL of water. Next,at a temperature of 80° C., the pressure was increased to the maximum of15 bar with hydrogen, and then the reaction mixture was stirred until nofurther absorption of hydrogen was found. To the resulting mixture wasadded 100 mL of toluene, and the catalyst was removed by filtration,followed by separation of the mixture into an organic phase and a waterphase with a separatory funnel. Then, purification of the organic phaseby fractional distillation gave 4-aminodiphenylamine in a yield of 91%.

An amount of 129.3 g of the 4-aminodiphenylamine, 120.2 g of the methylisobutyl ketone synthesized above, 0.77 g of a platinum catalyst (5% Pton carbon sulfide powder (hydrous product), water content: 55.26% bymass, produced by N.E. Chemcat Corporation), and 0.65 g of activatedcarbon (Taiko activated carbon S-type, produced by Futamura ChemicalCo., Ltd.) were introduced into a stirring autoclave and exposed to ahydrogen atmosphere. Then, the inside temperature of the autoclave wasraised from room temperature to 150° C. over about one hour.Subsequently, the hydrogen pressure was increased to 30 kgf/cm² (2.94MPa), and a reaction was allowed to proceed at the same temperature andthe same pressure while feeding the consumed amount of hydrogen.

After two hours from the start of increasing the hydrogen pressure,hydrogen was released from the autoclave to decrease the pressure tonormal pressure, while the reaction solution was cooled to roomtemperature. The reaction solution was filtrated to remove the catalystand the activated carbon. The resulting reaction product was subjectedto separation by high performance liquid chromatography to give4-(1,3-dimethylbutylamino)diphenylamine (antioxidant 6PPD-3) in a yieldof 99.4%.

Production Example 2 of Vulcanization Accelerator MBT from Aniline(Method of Synthesis of Vulcanization Accelerator MBT-3 in Table 2)

An amount of 93 g (1.0 mol) of the aniline obtained above (Synthesis 1of phenol from biomass material (using microorganism) and ProductionExample 2 of aniline from phenol), 80 g (1.1 mol) of the carbondisulfide obtained above (Method of preparing carbon disulfide withoutusing petroleum resources), and 16 g (1.0 mol) of sulfur were introducedinto a 300-mL pressurized reactor, and subjected to a reaction for twohours at a temperature of 250° C. under a pressure of 10 MPa, followedby cooling to 180° C. Thus, a crude product of 2-mercaptobenzothiazolewas obtained in an amount of 130 g (yield: 87%). Moreover, the obtainedcrude product of 2-mercaptobenzothiazole (purity: 79%) was dissolved inisopropanol at the boiling temperature in an inert gas atmosphere ofnitrogen. The resulting mixture was left at room temperature to cool. Aprecipitated product was separated by filtration, washed withisopropanol, and dried. Thus, a light yellow product(2-mercaptobenzothiazole with high purity (melting point: 180.1° C. to181.1° C., purity: 98.1%)) was obtained.

Production Example 2 of Vulcanization Accelerator CBS from Aniline(Method of Synthesis of Vulcanization Accelerator CBS-3 in Table 2)

The crude product of 2-mercaptobenzothiazole obtained above wasdissolved in an aqueous sodium hydroxide solution to prepare a 20%aqueous solution of a sodium salt of mercaptobenzothiazole. To thesolution was added an equivalent molar amount of cyclohexylamine. Themixed solution was further mixed with 100 mL of methanol at atemperature of 40° C. A 13% solution of sodium hypochlorite was allowedto act on the resulting mixture, in an amount of 1.2 times the molaramount of the sodium salt of mercaptobenzothiazole, followed by stirringfor one hour. After the reaction, water and the organic solvent wereremoved so that an oil of N-cyclohexyl-benzothiazolylsulfenamide wasobtained (yield: 93%).

(Preparation of Rubber Composition for Tread)

Chemical agents each in an amount shown in Process 1 in Table 2 wereintroduced into a Banbury mixer and kneaded for 5 minutes to raise theoutlet temperature to about 150° C. Thereafter, sulfur and vulcanizationaccelerators each in an amount shown in Process 2 were added to thekneaded mixture obtained in Process 1, and then kneaded with the Banburymixer for about three minutes to adjust the outlet temperature to 100°C. Thus, an unvulcanized rubber composition was obtained. The resultingunvulcanized rubber composition was molded into a tread shape, assembledwith other tire components and then vulcanized for 20 minutes at atemperature of 170° C. Thus, a test tire was produced.

Furthermore, each unvulcanized rubber composition was vulcanized for 20minutes at a temperature of 170° C. to prepare a vulcanized rubbersheet.

The chemical agents used above were as follows.

SBR: Nipol NS116 (solution-polymerized SBR, bound styrene content: 21%by mass, Tg: −25° C., produced by ZEON Corporation)

-   BR: BR150B (cis 1,4 bond content: 97% by mass, ML₁₊₄ (100° C.): 40),    produced by Ube Industries, Ltd.-   NR: RSS #3-   Silica: Ultrasil VN2 (BET specific surface area: 125 m²/g), produced    by Degussa-   Carbon black: Niteron #55S (carbon block made from coal-derived    heavy oil, N₂SA: 28×10³ m²/kg), produced by Nippon Steel Chemical    Carbon Co., Ltd.-   Silane coupling agent: Si69, produced by Degussa-   Mineral oil: PS-32, produced by Idemitsu Kosan Co., Ltd.-   Stearic acid: Kiri, produced by NOF Corporation-   Zinc oxide: zinc oxide #2, produced by Mitsui Mining & Smelting Co.,    Ltd.-   Antioxidant 6PPD-3: synthesized by the above method-   Antioxidant 6PPD-4: Nocrac 6C, produced by Ouchi Shinko Chemical    Industrial Co., Ltd.-   Antioxidant TMDQ-3: synthesized by the above method-   Antioxidant TMDQ-4: Nocrac 224, produced by Ouchi Shinko Chemical    Industrial Co., Ltd.-   Wax: SUNNOC Wax, produced by Ouchi Shinko Chemical Industrial Co.,    Ltd.-   Sulfur: sulfur powder, produced by Tsurumi Chemical Industry Co.,    Ltd.-   Vulcanization accelerator CBS-3: synthesized by the above method-   Vulcanization accelerator CBS-4: Nocceler CZ, produced by Ouchi    Shinko Chemical Industrial Co., Ltd.-   Vulcanization accelerator MBT-3: synthesized by the above method-   Vulcanization accelerator MBT-4: Nocceler M, produced by Ouchi    Shinko Chemical Industrial Co., Ltd.

The same evaluations as in Table 1 were made using the thus obtainedunvulcanized rubber compositions, vulcanized rubber sheets, and testtires. The test results are shown in Table 2.

TABLE 2 Comparative Example Example Composition Process 1 SBR 50 50(parts by mass) BR 30 30 NR 20 20 Silica 75 75 Carbon black 5 5 Silanecoupling agent 6 6 Mineral oil 10 10 Stearic acid 2 2 Zinc oxide 3 3Antioxidant 6PPD-3 1.5 Antioxidant 6PPD-4 1.5 Antioxidant TMDQ-3 0.5Antioxidant TMDQ-4 0.5 Wax 1.5 1.5 Process 2 Sulfur 1.5 1.5Vulcanization accelerator CBS-3 1.5 Vulcanization accelerator CBS-4 1.5Vulcanization accelerator MBT-3 0.2 Vulcanization accelerator MBT-4 0.2Evaluations Torque rise 101 100 Cure time 99 100 Breaking energy index100 100 Abrasion resistance index 100 100 Rolling resistance index 100100 Wet grip performance index 100 100 Dry grip performance index 100100

The rubber properties including vulcanization properties and breakingenergy index, and the tire properties including abrasion resistance,rolling resistance property, and wet/dry grip performance in Example areall equal to those in Comparative Example in which conventionalvulcanization accelerators and antioxidants that were synthesized fromfossil resources were used. This demonstrated that the Example makes itpossible to cope with depletion of fossil resources without anypractical problems.

REFERENCE SIGNS LIST

-   1 Gas introduction pipe-   2 Alcohol introduction pipe (material introduction pipe)-   3 Reaction tube-   4 Alcohol vapor layer (material vapor layer)-   5 Catalyst layer (reaction layer)-   6 Heater (electric furnace)-   7 Product trap-   8 a Cooling device-   8 b Heater-   9 Fractionator (fractioning pipe)-   10 Distillate trap (target product trap)-   11 Cooling device-   12 a, 12 b Reactant recirculation line-   21 Alcohol introduction pipe (material introduction pipe)-   22 Heater-   23 Dehydration reaction column-   24 Cooling device-   25 Heater-   26 Aromatic compound synthesis column-   27 Cooling device-   28 Reactant recirculation line

What is claimed is:
 1. A synthesis method for synthesizing aniline froma biomass material via phenol, said method comprising: synthesizing thephenol from the biomass resource; and synthesizing the aniline from thephenol.
 2. The synthesis method according to claim 1, wherein thebiomass material is a sugar or bioethanol.
 3. The synthesis methodaccording to claim 1, wherein the synthesis method is adapted to producethe phenol by a microorganism.
 4. The synthesis method according toclaim 1, wherein the synthesis method is adapted to produce the phenolby liquid culture of a microorganism.
 5. The synthesis method accordingto claim 3 or 4, wherein the microorganism is resistant to organicsolvents.
 6. The synthesis method according to claim 1, wherein thesynthesis method is adapted to produce the phenol from bioethanol as thebiomass material by using a solid acid catalyst.
 7. The synthesis methodaccording to claim 6, wherein the solid acid catalyst is a zeolite. 8.The synthesis method according to claim 6, wherein the solid acidcatalyst is an MFI zeolite.
 9. The synthesis method according to claim6, wherein the solid acid catalyst is an MFI zeolite carrying a memberselected from the group consisting of simple substances of copper,titanium, platinum and ruthenium, and compounds thereof.
 10. A rubberchemical for a tire, synthesized from the aniline obtained by thesynthesis method according to claim
 1. 11. The rubber chemical for atire according to claim 10, which is synthesized by further usingacetone obtained from a biomass material.
 12. The rubber chemical for atire according to claim 11, wherein the acetone is obtained byacetone-butanol fermentation of a sugar by a microorganism.
 13. Therubber chemical for a tire according to claim 12, wherein themicroorganism is Clostridium.
 14. The rubber chemical for a tireaccording to claim 12, wherein the microorganism comprises a gene ofClostridium introduced thereinto.
 15. The rubber chemical for a tireaccording to claim 14, wherein the gene encodes acetoacetatedecarboxylase, coenzyme A transferase, or thiolase.
 16. The rubberchemical for a tire according to claim 11, wherein the acetone isobtained by separation from pyroligneous acid.
 17. The rubber chemicalfor a tire according to claim 11, wherein the acetone is derived frombioethanol.
 18. A pneumatic tire produced using the rubber chemical fora tire according to claim 10.